Minimal geological methane emissions during the Younger Dryas-Preboreal abrupt warming event.

Methane (CH4) is a powerful greenhouse gas and plays a key part in global atmospheric chemistry. Natural geological emissions (fossil methane vented naturally from marine and terrestrial seeps and mud volcanoes) are thought to contribute around 52 teragrams of methane per year to the global methane source, about 10 per cent of the total, but both bottom-up methods (measuring emissions) and top-down approaches (measuring atmospheric mole fractions and isotopes) for constraining these geological emissions have been associated with large uncertainties. Here we use ice core measurements to quantify the absolute amount of radiocarbon-containing methane (14CH4) in the past atmosphere and show that geological methane emissions were no higher than 15.4 teragrams per year (95 per cent confidence), averaged over the abrupt warming event that occurred between the Younger Dryas and Preboreal intervals, approximately 11,600 years ago. Assuming that past geological methane emissions were no lower than today, our results indicate that current estimates of today's natural geological methane emissions (about 52 teragrams per year) are too high and, by extension, that current estimates of anthropogenic fossil methane emissions are too low. Our results also improve on and confirm earlier findings that the rapid increase of about 50 per cent in mole fraction of atmospheric methane at the Younger Dryas-Preboreal event was driven by contemporaneous methane from sources such as wetlands; our findings constrain the contribution from old carbon reservoirs (marine methane hydrates, permafrost and methane trapped under ice) to 19 per cent or less (95 per cent confidence). To the extent that the characteristics of the most recent deglaciation and the Younger Dryas-Preboreal warming are comparable to those of the current anthropogenic warming, our measurements suggest that large future atmospheric releases of methane from old carbon sources are unlikely to occur.

Gaseous elemental mercury emissions and CO(2) respiration rates in terrestrial soils under controlled aerobic and anaerobic laboratory conditions.

Mercury (Hg) levels in terrestrial soils are linked to the presence of organic carbon (C). Carbon pools are highly dynamic and subject to mineralization processes, but little is known about the fate of Hg during decomposition. This study evaluated relationships between gaseous Hg emissions from soils and carbon dioxide (CO(2)) respiration under controlled laboratory conditions to assess potential losses of Hg to the atmosphere during C mineralization. Results showed a linear correlation (r(2)=0.49) between Hg and CO(2) emissions in 41 soil samples, an effect unlikely to be caused by temperature, radiation, different Hg contents, or soil moisture. Stoichiometric comparisons of Hg/C ratios of emissions and underlying soil substrates suggest that 3% of soil Hg was subject to evasion. Even minute emissions of Hg upon mineralization, however, may be important on a global scale given the large Hg pools sequestered in terrestrial soils and C stocks. We induced changes in CO(2) respiration rates and observed Hg flux responses, including inducement of anaerobic conditions by changing chamber air supply from N(2)/O(2) (80% and 20%, respectively) to pure N(2). Unexpectedly, Hg emissions almost quadrupled after O(2) deprivation while oxidative mineralization (i.e., CO(2) emissions) was greatly reduced. This Hg flux response to anaerobic conditions was lacking when repeated with sterilized soils, possibly due to involvement of microbial reduction of Hg(2+) by anaerobes or indirect abiotic effects such as alterations in soil redox conditions. This study provides experimental evidence that Hg volatilization, and possibly Hg(2+) reduction, is related to O(2) availability in soils from two Sierra Nevada forests. If this result is confirmed in soils from other areas, the implication is that Hg volatilization from terrestrial soils is partially controlled by soil aeration and that low soil O(2) levels and possibly low soil redox potentials lead to increased Hg volatilization from soils.

Deposition of mercury species in the Ny-Alesund area (79 degrees N) and their transfer during snowmelt.

Arctic snowpacks are often considered as temporary reservoirs for atmospheric mercury (Hg) deposited during springtime deposition events (AMDEs). The fate of deposited species is of utmost importance because melt leads to the transfer of contaminants to snowmelt-fed ecosystems. Here, we examined the deposition, fate, and transfer of mercury species (total Hg (THg) and methylmercury (MeHg)) in an arctic environment from the beginning of mass deposition of Hg during AMDEs to the full melt of the snow. Following these events, important amounts of THg were deposited onto the snow surface with concentrations reaching 373 ng.L(-1) and estimated deposition fluxes of 200-2160 ng.m(-2). Most of the deposited Hg was re-emitted to the atmosphere via photochemical reactions. However, a fraction remained stored in the snow and we estimated that the spring melt contributed to an input of 1.5-3.6 kg.year(-1) of THg to the fjord (i.e., 8-21% of the fjord's THg content). A monitoring of MeHg in snow using a new technique (DGT sensors) is also presented.

Polar firn air reveals large-scale impact of anthropogenic mercury emissions during the 1970s.

Mercury (Hg) is an extremely toxic pollutant, and its biogeochemical cycle has been perturbed by anthropogenic emissions during recent centuries. In the atmosphere, gaseous elemental mercury (GEM; Hg degrees ) is the predominant form of mercury (up to 95%). Here we report the evolution of atmospheric levels of GEM in mid- to high-northern latitudes inferred from the interstitial air of firn (perennial snowpack) at Summit, Greenland. GEM concentrations increased rapidly after World War II from approximately 1.5 ng m(-3) reaching a maximum of approximately 3 ng m(-3) around 1970 and decreased until stabilizing at approximately 1.7 ng m(-3) around 1995. This reconstruction reproduces real-time measurements available from the Arctic since 1995 and exhibits the same general trend observed in Europe since 1990. Anthropogenic emissions caused a two-fold rise in boreal atmospheric GEM concentrations before the 1970s, which likely contributed to higher deposition of mercury in both industrialized and remotes areas. Once deposited, this toxin becomes available for methylation and, subsequently, the contamination of ecosystems. Implementation of air pollution regulations, however, enabled a large-scale decline in atmospheric mercury levels during the 1980s. The results shown here suggest that potential increases in emissions in the coming decades could have a similar large-scale impact on atmospheric Hg levels.

How elementary mercury reacts in the presence of halogen radicals and/or halogen anions: a DFT investigation.

Reactions of elementary mercury in the gas phase (GEM) have been investigated at the DFT level in the presence of halogen radicals and/or halogen anions. In the presence of radicals, the formation of HgX(3)* and HgX(4)* is predicted to be favourable. Moreover, in the presence of anions, the free-radical liberation is enhanced from these two species allowing the presence of halogen free radicals even without the presence of light radiation. This enhancement is associated with the formation of HgX(3)(-), which is predicted to be the most stable species. In solution, redox chemistry can occur and transform GEM in the presence of X(2). The redox potentials of the couples HgX(2)/Hg for X=Cl, Br and I were calculated to be 0.52, 0.48 and 0.04 V, respectively. This study gives new opportunities to elucidate the environmental chemistry of Hg in the polar regions. In these areas GEM has a unique and fast reactivity due to a combination of factors such as the polar sunrise, the presence of halogenated radicals, snow and ice surfaces and cold temperatures. This reactivity, known as atmospheric mercury depletion events (AMDEs), leads to the deposition of significant amounts of Hg(2+) in these regions. The reaction pathways of AMDEs are as yet unknown and the DFT approach may contribute to their elucidation and to the proposal of new mechanisms. Additionally, this study introduces hypotheses concerning the reactivity of GEM inside snowpacks.

Atmospheric mercury depletion event study in Ny-Alesund (Svalbard) in spring 2005. Deposition and transformation of Hg in surface snow during springtime.

A field campaign was conducted in Ny-Alesund (78 degrees 54'N, 11 degrees 53'E), Svalbard (Norway) during April and May 2005. An Atmospheric Mercury (Hg) Depletion Event (AMDE) was observed from the morning of April 24 until the evening of April 27. Transport of already Hg and ozone (O3) depleted air masses could explain this observed depletion. Due to a snowfall event during the AMDE, surface snow Hg concentrations increased two fold. Hg deposition took place over a short period of time corresponding to 3-4 days. More than 80% of the deposited Hg was estimated to be reemitted back to the atmosphere in the days following the event. During the campaign, we observed night and day variations in surface snow Hg concentrations, which may be the result of gaseous elemental mercury (GEM) oxidation to divalent Hg at the snow/air interface by daylight surface snow chemistry. Finally, a decrease in the reactive Hg (HgR) fraction of total Hg (HgT) in the surface snow was observed during spring. We postulate that the transformation of HgR to a more stable form may occur in Arctic snow during spring.

Mercury in the atmosphere, snow and melt water ponds in the North Atlantic Ocean during Arctic summer.

Atmospheric mercury speciation measurements were performed during a 10 week Arctic summer expedition in the North Atlantic Ocean onboard the German research vessel RV Polarstern between June 15 and August 29, 2004. This expedition covered large areas of the North Atlantic and Arctic Oceans between latitudes 54 degrees N and 85 degrees N and longitudes 16 degrees W and 16 degrees E. Gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P) were measured during this study. In addition, total mercury in surface snow and meltwater ponds located on sea ice floes was measured. GEM showed a homogeneous distribution over the open North Atlantic Ocean (median 1.53 +/- 0.12 ng/m3), which is in contrast to the higher concentrations of GEM observed over sea ice (median 1.82 +/- 0.24 ng/m3). It is hypothesized that this results from either (re-) emission of mercury contained in snow and ice surfaces that was previously deposited during atmospheric mercury depletion events (AMDE) in the spring or evasion from the ocean due to increased reduction potential at high latitudes during Arctic summer. Measured concentrations of total mercury in surface snow and meltwater ponds were low (all samples <10 ng/L), indicating that marginal accumulation of mercury occurs in these environmental compartments. Results also reveal low concentrations of RGM and Hg-P without a significant diurnal variability. These results indicate that the production and deposition of these reactive mercury species do not significantly contribute to the atmospheric mercury cycle in the North Atlantic Ocean during the Arctic summer.